Herbicidal compositions comprising benzoylpyrazoles and safeners

ABSTRACT

What is described are herbicidal compositions comprising herbicidal compounds of the formula I 
                 
 
and a compound which acts as safener. In the formula I, the symbols R 1  to R 4  denote hydrogen, halogen, alkyl and haloalkyl.

The invention relates to the technical field of the crop protectionproducts, in particular herbicide/antidote combinations (activeingredient/safener combinations) which are suitable for use againstcompeting harmful plants in crops of useful plants.

A large number of herbicidal active ingredients are known as inhibitorsof the enzyme p-hydroxyphenylpyruvate dioxygenase (HPPD). Only recently,more such active ingredients were disclosed, for example in WO 99/58509and DE 10016116.2.

As is the case with many other herbicidal active ingredients, these HPPDinhibitors are also not always sufficiently well tolerated by (i.e. notsufficiently selective in) some important crop plants such as corn, riceor cereals, so that their use is very limited. They can therefore not beemployed in some crops, or only at such low application rates that thedesired broad herbicidal activity against harmful plants is not ensured.Specifically, many of the abovementioned herbicides cannot be employedas fully selective herbicides against harmful plants in corn, rice,cereals, sugar cane and some other crops.

To overcome these disadvantages, it is known to employ herbicidal activeingredients in combination with what is known as a safener or antidote.Thus, for example, WO 99/66795 and WO 00/30447 describes variouscombinations of a large number of HPPD inhibitors with a multiplicity ofsafeners. Inter alia, WO 00/30447 also describes benzoylpyrazoles incombination with different safeners.

A safener is understood as meaning a compound which compensates for, orreduces, the phytotoxic properties of a herbicide with regard to usefulplants, without substantially reducing the herbicidal activity againstharmful plants.

Finding a safener for a specific group of herbicides remains a difficulttask since the mechanisms by which a safener reduces the harmful actionof herbicides are not known in detail. The fact that a compound incombination with a specific herbicide acts as safener therefore allowsno conclusions to be drawn as to whether such a compound also has asafener action with other groups of herbicides. Thus, it has emergedwhen safeners are used for protecting the useful plants from herbicidedamage that the safeners may still exhibit certain disadvantages in manycases. These include:

-   -   the safener reduces the activity of the herbicide against the        harmful plants,    -   the useful-plant protecting properties are insufficient,    -   the spectrum of the useful plants in which the safener/herbicide        is to be employed is not sufficiently wide in combination with a        given herbicide,    -   a given safener cannot be combined with a sufficiently large        number of herbicides.

It was an object of the present invention to provide furthercombinations of herbicides from the group of the HPPD inhibitors withsafeners which are suitable for increasing the selectivity of theseherbicides with regard to important crop plants.

There have now been found novel combinations of specific herbicides fromthe group of the HPPD inhibitors, specifically from the group of thebenzoylpyrazoles which have selected substituents attached in the 2 and4-positions of the benzoyl moiety, with some selected safeners whichincrease the selectivity of these herbicides with regard to importantcrop plants.

The invention therefore relates to a herbicidally active compositioncomprising

-   A) a herbicidally effective amount of one or more compounds of the    formula (I), if appropriate also in the form of their salts:    where    -   R¹ is methyl or ethyl;    -   R² is trifluoromethyl, fluorine, chlorine or bromine;    -   R³ is hydrogen or methyl;    -   R⁴ is methyl or ethyl;    -   R⁵ is hydrogen, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,        phenylsulfonyl, 4-methylphenylsulfonyl, benzyl, benzoylmethyl,        nitrobenzoylmethyl or 4-fluorobenzoylmethyl and    -   n is 0, 1, or 2, and-   B) an antidote-effective amount of at least one compound    (component B) from one of the groups B1 to B6:-   B1 compounds of the formula II:    where R⁶ and R⁷ independently of one another are hydrogen or    (C₁-C₄)-alkyl;-   B2 compounds of the formula III:    where R⁸ is hydrogen or (C₁-C₄)-alkyl;-   B3 oxabetrinil, fluxofenim, fenclorim, flurazole,    cloquintocet-mexyl, dichlormid, benoxacor, furilazole,    4-dichloroacetyl-1-oxa-4-aza-spiro[4,5]decane (AD-67);-   B4 1,8-naphthalic anhydride, methyl diphenylmethoxyacetate,    cyanomethoxyimino(phenyl)acetonitrile (cyometrinil),    2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),    N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),    1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,    1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,    1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,    1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,    1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate    (lactidichlor) and their salts and esters, preferably (C₁-C₈),    3-dichloroacetyl-2,2,5-trimethyloxazolidine, 1,3-dimethylbut-1-yl    (5-chloro-8-quinolineoxy)acetate, 4-allyloxybutyl    (5-chloro-8-quinolineoxy)acetate, 1-allyloxyprop-2-yl    (5-chloro-8-quinolineoxy)acetate, ethyl    (5-chloro-8-quinolineoxy)acetate, methyl    (5-chloro-8-quinolineoxy)acetate, allyl    (5-chloro-8-quinolineoxy)acetate, 2-(2-propylideneiminooxy)-1-ethyl    (5-chloro-8-quinolineoxy)acetate, 2-oxoprop-1-yl    (5-chloro-8-quinolineoxy)acetate;-   B5 acylsulfamoylbenzamides of the formula (IV), if appropriate also    in salt form:    where    -   X is CH or N;    -   R⁹ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,        (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, where the four last mentioned        radicals are unsubstituted or substituted by one or more        identical or different substituents from the group consisting of        halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,        (C₁-C₂)-alkylsulfinyl, (C₁-C₂)-alkylsulfonyl,        (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxycarbonyl,        (C₁-C₄)-alkylcarbonyl and, in the case of cyclic radicals, also        (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl;    -   R¹⁰ is hydrogen, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl,        (C₂-C₆)-alkynyl, where the three last mentioned radicals are        unsubstituted or substituted by one or more identical or        different substituents from the group consisting of halogen,        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and (C₁-C₄)-alkylthio, or    -   R⁹ and R¹⁰ together with the nitrogen atom carrying them form a        pyrrolidinyl or piperidinyl radical;    -   R¹¹ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl or        (C₁-C₄)-alkynyl;    -   R¹² are identical or different and are halogen, nitro,        (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy,        (C₁-C₄)-alkoxy, cyano, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,        (C₁-C₄)-alkylsulfonyl,    -   m is 0, 1 or 2;-   B6 N-acylsulfonamides of the formula (V) and their salts:    where    -   R¹³ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, where each        of the 2 last mentioned radicals is unsubstituted or substituted        by one or more substituents from the group consisting of        halogen, (C₁-C₄)-alkoxy, halo-(C₁-C₆)-alkoxy and        (C₁-C₄)-alkylthio and, in the case of cyclic radicals, also        (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl,    -   R¹⁴ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, such as        trifluoromethyl, halo-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy or        (C₁-C₄)-alkylthio,    -   t is 1 or 2,        including the stereoisomers and the agriculturally useful salts.

Herbicidally active amount for the purposes of the invention refers toan amount of one or more herbicides suitable for having an adverseeffect on plant growth.

Antidote-effective amount for the purposes of the invention refers to anamount of one or more safeners suitable for at least partiallycounteracting the phytotoxic effect of a herbicide or herbicide mixtureon a useful plant.

Unless specifically defined otherwise, the definitions given hereinbelowgenerally apply to the radicals in the formula (I).

Alkyl, also in the composite meanings such as alkoxy or haloalkoxy,denotes, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or2-butyl, n-pentyl and n-hexyl. The meanings of alkenyl and alkynyl areto be understood analogously.

Formulae (I) to (V) also encompass all stereoisomers which have the sametopological linkage of the atoms, and their mixtures. Such compoundscontain one or more asymmetric carbon atoms and/or double bonds. Thepossible enantiomers and/or diastereomers, defined by their specificspatial form, can be obtained from stereoisomer mixtures by customarymethods or else be prepared by stereoselective reactions in combinationwith the use of stereochemically pure starting materials.

Suitable herbicidally active compounds are, in accordance with theinvention, those compounds of the formula (I) which cannot be employedon their own, or which cannot be employed optimally, in crops of usefulplants such as cereal crops, rice or corn since they cause too muchdamage to the crop plants.

Herbicides of the formula (I) are known, for example, from DE10016116.2. The compounds of group B1 are known from U.S. Pat. No.5,703,008 and U.S. Pat. No. 5,700,758. The compounds of group B2 areknown from WO 95/07897 and the literature cited therein. The chemicalstructures of the active compounds of group B3, referred to by theircommon names, are known, for example, from “The Pesticide Manual”, 12thedition, 2000, British Crop Protection Council. The compounds of groupB4 are known, for example, from EP-A-0 086 750, EP-A-0 94349 (U.S. Pat.No. 4,902,340), EP-A-0 191736 (U.S. Pat. No. 4,881,966) and EP-A-0 492366 and the literature cited therein. The compounds of group B5 aredescribed in WO-A-97/45016, those of group B6 in the German patentapplication 197 42 951.3. The publications cited above contain detailedinformation on preparation processes and starting materials. Thesepublications are expressly referred to; by reference, they areincorporated into this description.

For the purposes of the present application, the terms “herbicidalcompositions” and “herbicide/safener combinations” are to be consideredas having the same meaning.

Preference is given to herbicidal compositions comprising one of theherbicidally active compounds of the formula (Ia) comprising thecompounds A1, A2, A3 and A4:

(Ia)

No. R¹ R² R³ R⁴ R⁵ n (A1) CH₃ CF₃ H CH₃ H 2 (A2) CH₃ CF₃ CH₃ CH₃ H 2(A3) CH₃ CF₃ CH₃ CH₂CH₃ H 2 (A4) CH₃ CF₃ H CH₂CH₃ H 2

Preference is also given to herbicidal compositions comprising, assafener, one or more compounds from the group comprising the compoundsmefenpyr-diethyl (B1.1), oxabetrinil (B3.1), fluxofenim (B3.2),fenclorim (B3.3), flurazole (B3.4), cloquintocet-mexyl (B3.5),dichlormid (B3.6), benoxacor (B3.7), furilazole (B3.8) and the compoundsB2.1, B2.2, B2.3, B5.1, B5.2, B5.3, B5.4, B5.5, B5.6 and B5.7:

Particular preference is given to herbicidal compositions comprising thefollowing combinations of two compounds (A)+(B):

-   -   (A1)+(B1.1), (A1)+(B2.1), (A1)+(B2.2), (A1)+(B2.3), (A1)+(B3.1),        (A1)+(B3.2), (A1)+(B3.3), (A1)+(B3.4), (A1)+(B3.5), (A1)+(B3.6),        (A1)+(B3.7), (A1)+(B3.8), (A1)+(B5.1), (A1)+(B5.2), (A1)+(B5.3),        (A1)+(B5.4), (A1)+(B5.5), (A1)+(B5.6), (A1)+(B5.7);    -   (A2)+(B1.1), (A2)+(B2.1), (A2)+(B2.2), (A2)+(B2.3), (A2)+(B3.1),        (A2)+(B3.2), (A2)+(B3.3), (A2)+(B3.4), (A2)+(B3.5), (A2)+(B3.6),        (A2)+(B3.7), (A2)+(B3.8), (A2)+(B5.1), (A2)+(B5.2), (A2)+(B5.3),        (A2)+(B5.4), (A2)+(B5.5), (A2)+(B5.6), (A2)+(B5.7);    -   (A3)+(B1.1), (A3)+(B2.1), (A3)+(B2.2), (A3)+(B2.3), (A3)+(B3.1),        (A3)+(B3.2), (A3)+(B3.3), (A3)+(B3.4), (A3)+(B3.5), (A3)+(B3.6),        (A3)+(B3.7), (A3)+(B3.8), (A3)+(B5.1), (A3)+(B5.2), (A3)+(B5.3),        (A3)+(B5.4), (A3)+(B5.5), (A3)+(B5.6), (A3)+(B5.7);    -   (A4)+(B1.1), (A4)+(B2.1), (A4)+(B2.2), (A4)+(B2.3), (A4)+(B3.1),        (A4)+(B3.2), (A4)+(B3.3), (A4)+(B3.4), (A4)+(B3.5), (A4)+(B3.6),        (A4)+(B3.7), (A4)+(B3.8), (A4)+(B5.1), (A4)+(B5.2), (A4)+(B5.3),        (A4)+(B5.4), (A4)+(B5.5), (A4)+(B5.6), (A4)+(B5.7).

The compounds mentioned herein as safeners (antidotes) reduce orcompensate for phytotoxic effects which may occur when using theherbicidally active compounds of the formula (I) in crops of usefulplants without essentially adversely affecting the efficacy of theseherbicidally active compounds against harmful plants. Thus, the field ofapplication of conventional crop protection agents can be widenedconsiderably and extended to, for example, crops such as wheat, barley,rice and corn in which the use of the herbicides has previously not beenpossible or only with limitations, that is to say at low dosages with anarrow spectrum of action.

The herbicidally active compounds and the safeners mentioned can beapplied together (as readymix or by the tank mix method) or sequentiallyin any desired sequence. The weight ratio of safener to herbicidallyactive compound may vary within wide limits and is preferably in therange of from 1:100 to 100:1, in particular from 1:10 to 10:1. Theoptimum amounts of herbicidally active compound and safener depend ineach case on the type of the herbicidally active compound used or on thesafener used and on the nature of the plant stock to be treated and canbe determined in each individual case by simple routine preliminaryexperiments.

The combinations according to the invention are preferably used forcontrolling unwanted harmful plants in corn and cereal crops such as,for example, wheat, rye, barley, oats, rice, sorghum, but also cotton,sugar beet, sugar cane and soybean, preferably cereals, rice and corn.

Depending on their properties, the safeners employed in accordance withthe invention may be used for pretreating the seed of the crop plant(seed dressing) or introduced into the seed furrows prior to sowing orused together with the herbicide before or after emergence of theplants. Pre-emergence treatment includes not only the treatment of thearea under cultivation before sowing, but also the treatment of the sownsoil which does not yet sustain vegetation. Preferred is the applicationtogether with the herbicide. Tank mixes or readymixes may be employedfor this purpose.

The safener application rates required may vary within wide limits,depending on the indication and the herbicidally active compound used;they are, as a rule, in the range of from 0.001 to 5 kg, preferably from0.005 to 0.5 kg, of active compound per hectare.

The present invention therefore also relates to a method of protectingcrop plants from phytotoxic side effects of herbicides of the formula(I), which comprises applying an antidote-effective amount of one ormore compounds of component B before, after or simultaneously with theherbicidally active compound A of the formula (I) to the plants, plantseeds or the area under cultivation.

The herbicide/safener combination according to the invention may also beemployed for controlling harmful plants in crops of known geneticallymodified plants or genetically modified plants yet to be developed. As arule, the transgenic plants are distinguished by particularlyadvantageous properties, for example by resistances to certain cropprotection agents, resistances to plant diseases or to causative agentsof plant diseases such as specific insects or microorganisms such asfungi, bacteria or viruses. Other particular properties concern forexample the harvested crop with regard to quantity, quality,storability, composition and specific constituents. Thus, transgenicplants are known with an increased starch content or a modified starchquality, or those with a different fatty acid composition of theharvested crop.

Preferred is the use of the combinations according to the invention ineconomically important crops of transgenic useful plants, for example ofcereals such as wheat, barley, rye, oats, millet rice, cassava and corn,or else crops of sugar beet, sugar cane, cotton, soybean, oilseed rape,potato, tomato, pea and other vegetables.

When the combinations according to the invention are used in transgeniccrops, effects in addition to the effects to be observed against harmfulplants in other crops are frequently found, which are specific forapplication in the particular transgenic crop, for example a modified orspecifically widened weed spectrum which can be controlled, modifiedapplication rates which may be employed for the application, preferablygood combinability with the herbicides to which the transgenic crop isresistant, and an effect on growth and yield of the transgenic cropplants.

The invention thus also relates to the use of the combination accordingto the invention for controlling harmful plants in transgenic cropplants.

The safeners of component B and their combinations with one or more ofthe abovementioned herbicidally active compounds of the formula (I) canbe formulated in various ways, depending on the prevailing biologicaland/or chemico-physical parameters. Suitable possibilities offormulation are, for example, wettable powders (WP), emulsifiableconcentrates (EC), water-soluble powders (SP), water-solubleconcentrates (SL), concentrated emulsions (BW) such as oil-in-water andwater-in-oil emulsions, sprayable solutions or emulsions, capsulesuspensions (CS), oil- or water-based dispersions (SC), suspoemulsions,suspension concentrates, dusts (DP), oil-miscible solutions (OL),seed-dressing products, granules (GR) in the form of microgranules,spray granules, coated granules and absorption granules, granules forsoil application or broadcasting, water-soluble granules (SG),water-dispersible granules (WG), ULV formulations, microcapsules andwaxes.

These individual formulation types are known in principle and aredescribed, for example, in: Winnacker-Küchler, “Chemische Technologie”[Chemical engineering], Volume 7, C. Hauser Verlag Munich, 4th Ed.,1986; Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker N.Y.,1973; K. Martens, “Spray Drying Handbook”, 3rd Ed. 1979, G. Goodwin Ltd.London.

The formulation auxiliaries which may be required, such as inertmaterials, surfactants, solvents and further additives are likewiseknown and described, for example, in: Watkins, “Handbook of InsecticideDust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley &Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y.1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp.,Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface ActiveAgents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt,“Grenzflächenaktive Äthylenoxidaddukte” [Surface-active ethylene oxideadducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler,“Chemische Technologie”, Volume 7, C. Hauser Verlag Munich, 4th Ed.1986.

Based on these formulations, combinations with other crop protectantssuch as insecticides, acaricides, herbicides, fungicides, and withsafeners, fertilizers and/or growth regulators may also be prepared, forexample in the form of a readymix or a tank mix.

Wettable powders are preparations which are uniformly dispersible inwater and which, besides the active compound, additionally compriseionic and/or nonionic surfactants (wetters, dispersants), for examplepolyoxethylated alkylphenols, polyoxethylated fatty alcohols,polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates,alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium2,2′-dinaphthylmethane-6,6′-disulfonate, sodiumdibutylnaphthalene-sulfonate, or else sodium oleoylmethyltaurinate, inaddition to a diluent or inert substance. To prepare the wettablepowders, the herbicidally active compounds are ground finely, forexample in customary apparatuses such as hammer mills, blower mills andair-jet mills, and simultaneously or subsequently mixed with theformulation auxiliaries.

Emulsifiable concentrates are prepared for example by dissolving theactive compound in an organic solvent, for example butanol,cyclohexanone, DMF or else high-boiling hydrocarbons such as saturatedor unsaturated aliphatic or alicyclic substances, aromatic substances ormixtures of these organic solvents with addition of one or more ionicand/or nonionic surfactants (emulsifiers). The following are examples ofemulsifiers which may be used: calcium alkylarylsulfonates such ascalcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fattyacid polyglycol esters, alkylaryl polyglycol ethers, fatty alcoholpolyglycol ethers, propylene oxide/ethylene oxide condensates, alkylpolyethers, sorbitan esters such as, for example, sorbitan fatty acidesters or polyoxyethylene sorbitan esters such as polyoxyethylenesorbitan fatty acid esters. Dusts are obtained in general by grindingthe active compound with finely divided solid materials, for exampletalc, natural clays such as kaolin, bentonite and pyrophyllite, ordiatomaceous earth.

Suspension concentrates may be water- or oil-based. They can be preparedfor example by wet-milling by means of commercially available beadmills, if appropriate with addition of surfactants as, for example, havealready been listed above in the case of the other formulation types.

Emulsions, for example oil-in-water emulsions (EW), can be prepared forexample by means of stirrers, colloid mills and/or static mixers usingaqueous organic solvents and, if appropriate, surfactants as, forexample, have already been listed above in the case of the otherformulation types.

Granules can be produced either by spraying the active compound ontoadsorptive granulated inert material or by applying active compoundconcentrates to the surface of carriers such as sand, kaolinite or ofgranulated inert material by means of binders, for example polyvinylalcohol, sodium polyacrylate or else mineral oils. Suitable activecompounds may also be granulated in the manner which is conventional forthe production of fertilizer granules, if desired as a mixture withfertilizers.

As a rule, water-dispersible granules are prepared by the customarymethods such as spray-drying, fluidized-bed granulation, diskgranulation, mixing by means of high-speed mixers, and extrusion withoutsolid inert material.

To prepare disk, fluidized-bed, extruder and spray granules, see, forexample, methods in “Spray-Drying Handbook” 3rd ed. 1979, G. GoodwinLtd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering1967, pages 147 et seq.; “Perry's Chemical Engineer's Handbook”, 5thEd., McGraw-Hill, New York 1973, pp. 8-57.

For further details on the formulation of crop protection agents see,for example, G. C. Klingman, “Weed Control as a Science”, John Wiley andSons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans,“Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications,Oxford, 1968, pages 101-103.

As a rule, the agrochemical preparations comprise from 0.1 to 99% byweight, in particular from 0.1 to 95% by weight, of active compoundsfrom group B or of the herbicide/antidote active compound mixture (I) Band from 1 to 99.9% by weight, in particular from 5 to 99.8% by weight,of a solid or liquid additive and from 0 to 25% by weight, in particularfrom 0.1 to 25% by weight, of a surfactant.

In wettable powders, the active compound concentration is, for example,from approximately 10 to 90% by weight, the remainder to 100% by weightbeing composed of customary formulation components. In the case ofemulsifiable concentrates, the concentration amounts to approximately 1to 80% by weight. Formulations in the form of dusts comprise fromapproximately 1 to 20% by weight of active compounds, sprayablesolutions from approximately 0.2 to 20% by weight of active compounds.In the case of granules such as water-dispersible granules, the activecompound content depends partly on whether the active compound is inliquid or solid form. As a rule, the active compound content in thewater-dispersible granules is between 10 and 90% by weight.

In addition, the active compound formulations mentioned comprise, ifappropriate, the adhesives, wetters, dispersants, emulsifiers,penetrants, preservatives, antifreeze agents, solvents, fillers,carriers, colorants, antifoams, evaporation inhibitors, pH regulatorsand viscosity regulators which are conventional in each case.

The necessary application rate of the herbicides of the formula (I)varies with the external conditions such as, inter alia, temperature,humidity and the type of the herbicide used. It can be varied withinwide limits, for example between 0.001 and 10.0 kg/ha or more of activesubstance, but it is preferably between 0.005 and 5 kg/ha.

The examples which follow illustrate the invention:

A Formulation examples

-   a) A dust is obtained by mixing 10 parts by weight of a compound of    group B or of an active compound mixture of a herbicidally active    compound of the formula (I) and a compound of group B and 90 parts    by weight of talc as inert substance and comminuting the mixture in    a hammer mill.-   b) A wettable powder which is readily dispersible in water is    obtained by mixing 25 parts by weight of a compound of group B or of    an active compound mixture of a herbicidally active compound of the    formula (I) and a compound of group B, 64 parts by weight of    kaolin-containing quartz as inert material, 10 parts by weight of    potassium lignosulfonate and 1 part by weight of sodium    oleoylmethyltaurinate as wetter and dispersant and grinding the    mixture in a pinned-disk mill.-   c) A dispersion concentrate which is readily dispersible in water is    obtained by mixing 20 parts by weight of a compound of group B or of    an active compound mixture of a herbicidally active compound of the    formula (I) and a compound of group B, 6 parts by weight of    alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of    isotridecanol polyglycol ether (8 EO) and 71 parts by weight of    paraffinic mineral oil (boiling range for example approx. 255 to    above 277° C.) and grinding the mixture in a bowl mill to a fineness    of below 5 microns.-   d) An emulsifiable concentrate is obtained from 15 parts by weight    of a compound of group B or of an active compound mixture of a    herbicidally active compound of the formula (I) and a compound of    group B, 75 parts by weight of cyclohexanone as solvent and 10 parts    by weight of oxethylated nonylphenol as emulsifier.-   e) Water-dispersible granules are obtained by mixing

75 parts by weight of a compound of group B or of an active compoundmixture of a herbicidally active compound of the formula (I) and acompound of group B, 10 parts by weight of calcium lignosulfonate, 5parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinylalcohol and 7 parts by weight of kaolin,grinding the mixture on a pinned-disk mill and granulating the powder ina fluidized bed by spraying on water as granulation liquid.

-   f) Water-dispersable granules are also obtained by homogenizing and    precomminuting

25 parts by weight of a compound of group B or of an active compoundmixture of a herbicidally active compound of the formula (I) and acompound of group B, 5 parts by weight of sodium2,2′-dinaphthylmethane-6,6′-disulfonate, 2 parts by weight of sodiumoleoylmethyltaurinate, 1 parts by weight of polyvinyl alcohol, 17 partsby weight of calcium carbonate and 50 parts by weight of waterin a colloid mill, subsequently milling the mixture in a bead mill andatomizing and drying the resulting suspension in a spray tower by meansof a single-substance nozzle.B Biological Examples

Post-emergence experiments:

Seeds of useful plants are placed in soil in the open and covered withsoil. At the three-leaf stage, i.e. approximately three weeks after thestart of cultivation, the plants are treated with the herbicidesformulated as emulsifiable concentrates or dusts and safeners in theform of aqueous dispersions or suspensions or emulsions at anapplication rate of 300 to 800 l of water per ha (converted) at variousdosages. The damage to the useful plants is scored visually 14 daysafter the treatment. The results demonstrate that the damage in theuseful plants can be reduced considerably by using the compositionsaccording to the invention comprising herbicide and safener incomparison with using the herbicide only. Depending on the rate ofapplication, the species of the useful plant and the type of thecomposition according to the invention, the damage is reduced by up to100% in comparison with using the herbicide only.

The test results of some herbicidal compositions according to theinvention comprising herbicide and safener are shown in the tablesbelow.

Table 2 shows the reduction of the damage to the crop plant wheat whenusing the compositions according to the invention, compared to the useof the herbicide on its own. Table 3 shows the reduction of the damageto different cultivars of the crop plant corn when using thecompositions according to the invention, compared to the use of theherbicide on its own.

TABLE 1 Stucture

TABLE 2 Compound Dosage [g of a.l./ha] Reduction of damage in wheat A2 +B1.1 75 + 15 −56%

TABLE 3 Compound Dosage [g of a.i./ha] Reduction of damage in corn A2 +B5.1 200 + 100 −100% (variety “DEA”) A2 + B2.3 150 + 150 −100% (variety“HELIX”)

1. A herbicidal composition, comprising A) a herbicidally effectiveamount of one or more compounds of the formula (I), or stereoisomers oragriculturally useful salts therefof,

where R¹ is methyl or ethyl; R² is trifluoromethyl, fluorine, chlorineor bromine; R³ is hydrogen or methyl; R⁴ is methyl or ethyl; R⁵ ishydrogen, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,phenylsulfonyl, 4-methylphenylsulfonyl, benzyl, benzoylmethyl,nitrobenzoylmethyl or 4-fluorobenzoylmethyl and n is 0, 1, or 2, and B)an antidote-effective amount of at least one safener compound from groupto B5: B5 acylsulfamoylbenzamides of the formula (IV), or stereoisomersor agriculturally useful salts therefof,

where X is CH or N; R⁹ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,(C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, where the four last mentioned radicalsare unsubstituted or substituted by one or more identical or differentsubstituents from the group consisting of halogen, (C₁-C₆)-alkoxy,(C₁-C₆)-haloalkoxy, (C₁-C₂)-alkylsulfinyl, (C₁-C₂)-alkylsulfonyl,(C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylcarbonyl and,in the case of cyclic radicals, also (C₁-C₄)-alkyl and(C₁-C₄)-haloalkyl; R¹⁰ is hydrogen, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl,(C₂-C₆)-alkynyl, where the three last mentioned radicals areunsubstituted or substituted by one or more identical or differentsubstituents from the group consisting of halogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy and (C₁-C₄)-alkylthio, or R⁹ and R¹⁰ together with thenitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical;R¹¹ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl or (C₁-C₄)-alkynyl; R¹²are identical or different and are halogen, nitro, (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy, cyano,(C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfonyl, m is 0,1 or
 2. 2. A herbicidal composition as claimed in claim 1, where R¹ ismethyl; R² is trifluoromethyl; R³ is hydrogen or methyl; R⁴ is methyl orethyl; R⁵ is hydrogen and n is
 2. 3. A herbicidal composition as claimedin claim 1, wherein the weight ratio herbicide:safener is from 1:100 to100:1.
 4. A method for controlling harmful plants in crops of usefulplants, which comprises applying a herbicidally effective amount of aherbicide/safener combination as claimed in claim 1 onto the harmfulplants, plants, plant seeds or the area on which the plants grow.
 5. Amethod as claimed in claim 4, wherein the plants originate from thegroup consisting of corn, wheat, rye, barley, oats, rice, sorghum,cotton, sugar cane and soya.
 6. A method as claimed in claim 4, whereinthe plants are genetically modified.
 7. A herbicidal composition asclaimed in claim 1, where R¹is methyl; R² is trifluoromethyl; R³ ismethyl; R⁴ is methyl; R⁵ is hydrogen; and n is
 2. 8. A herbicidalcomposition as claimed in claim 1, where in the compound of formula IV,X is CH; R⁹ is cyclopropyl; R¹⁰ is hydrogen; R¹¹ is hydrogen; R¹² ismethoxy; and m is
 1. 9. A herbicidal composition as claimed in claim 1,wherein R¹ is methyl; R² is trifluoromethyl; R³ is methyl; R⁴ is methyl;R⁵ is hydrogen; n is 2; X is CH; R⁹ is cyclopropyl; R¹⁰ is hydrogen; R¹¹is hydrogen; R¹² is methoxy; and m is 1.